Silyl-containing thermosetting networks and methods of degradation

Patent metadata

Field	Value
Publication number	US-11401368-B2
Application number	US-202016917142-A
Country	US
Kind code	B2
Filing date	Jun 30, 2020
Priority date	Dec 15, 2016
Publication date	Aug 2, 2022
Grant date	Aug 2, 2022

Abstract

A process of: providing a polyfunctional compound selected from polyisocyanate, polyacrylate, and polyepoxy; and reacting the polyfunctional compound with a hydroxyl- or amine-terminated silyl-containing compound. The polyfunctional compound and the silyl-containing compound are at least difunctional. A thermoset made by this process.

First claim

What is claimed is:

1. A thermoset made by a process comprising:
providing a polyfunctional compound selected from polyisocyanate, polyacrylate, and polyepoxy; and
reacting the polyfunctional compound with a hydroxyl- or amine-terminated silyl-containing compound;
wherein the polyfunctional compound and the silyl-containing compound are at least difunctional;
wherein the silyl-containing compound has the formula
SiR 1 n [R 3 —(O—CO—X—R 3 ) m —X′] 4-n ;

wherein each X is independently selected from —O— and —NR 2 —;
wherein each X′ is independently selected from —OH and —NHR 2 ;
wherein each R 1 is independently selected from alkyl groups and aryl groups;
wherein each R 2 is independently selected from —H, alkyl groups, and aryl groups;
wherein each R 3 is an independently selected alkylene group;
wherein n is 0, 1, or 2; and
wherein each m is an independently selected positive integer.

2. The thermoset of claim 1 , wherein the polyfunctional compound is a polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate, a cycloaliphatic polyisocyanate, an isocyanate homopolymer, or an isocyanate-functional pre-polymer.

3. The thermoset of claim 1 , wherein the polyisocyanate is an aliphatic trimer based on hexamethylene diisocyanate.

4. The thermoset of claim 1 , wherein the polyfunctional compound is an epoxy-functional dimethylpolysiloxane, an epoxy-functional polydimethyldiphenylsiloxane, an aliphatic epoxy, an aromatic epoxy, a cycloaliphatic epoxy, an acrylate-functional dimethylpolysiloxane, or 1,6-hexanedioldiacrylate.

5. The thermoset of claim 1 , wherein the silyl-containing compound is
Si(Ph) 2 (CH 2 CH 2 OCON(CH 3 )CH 2 CH 2 OH) 2 .

6. The thermoset of claim 1 , wherein each R 3 group is ethylene or propylene.

7. The thermoset of claim 1 , wherein the polyfunctional compound is reacted with a hydroxyl-functional or amine-functional material with at least one hydroxyl or amine group.

8. The thermoset of claim 1 , wherein the thermoset comprises at least 5 wt. % of the silyl-containing compound.

9. A method comprising:
reacting the thermoset of claim 1 with a fluoride salt, an acid, or a base to cleave the silicon-carbon bonds in the thermoset.

10. The method of claim 9 ;
wherein the fluoride salt is tetrabutylammonium fluoride, stannous fluoride, potassium fluoride, or sodium fluoride;
wherein the acid is a Lewis acid or Bronsted acid; or
wherein the base is a Lewis base or Bronsted base.

11. A method of making a thermoset comprising:
providing a polyfunctional compound selected from polyisocyanate, polyacrylate, and polyepoxy; and
reacting the polyfunctional compound with a hydroxyl- or amine-terminated silyl-containing compound;
wherein the polyfunctional compound and the silyl-containing compound are at least difunctional;
wherein the silyl-containing compound has the formula
SiR 1 n [R 3 —(O—CO—X—R 3 ) m —X′] 4-n ;

wherein each X is independently selected from —O— and —NR 2 —;
wherein each X′ is independently selected from —OH and —NHR 2 ;
wherein each R 1 is independently selected from alkyl groups and aryl groups;
wherein each R 2 is independently selected from —H, alkyl groups, and aryl groups;
wherein each R 3 is an independently selected alkylene group;
wherein n is 0, 1, or 2; and
wherein each m is an independently selected positive integer.

12. The method of claim 11 , wherein the polyfunctional compound is a polyisocyanate, an aliphatic polyisocyanate, an aromatic polyisocyanate, a cycloaliphatic polyisocyanate, an isocyanate homopolymer, or an isocyanate-functional pre-polymer.

13. The method of claim 11 , wherein the polyisocyanate is an aliphatic trimer based on hexamethylene diisocyanate.

14. The method of claim 11 , wherein the polyfunctional compound is an epoxy-functional dimethylpolysiloxane, an epoxy-functional polydimethyldiphenylsiloxane, an aliphatic epoxy, an aromatic epoxy, a cycloaliphatic epoxy, an acrylate-functional dimethylpolysiloxane, or 1,6-hexanedioldiacrylate.

15. The method of claim 11 , wherein the silyl-containing compound is
Si(Ph) 2 (CH 2 CH 2 OCON(CH 3 )CH 2 CH 2 OH) 2 .

16. The method of claim 11 , wherein each R 3 group is ethylene or propylene.

17. The method of claim 11 , wherein the polyfunctional compound is reacted with a hydroxyl-functional or amine-functional material with at least one hydroxyl or amine group.

18. The method of claim 11 , wherein the thermoset comprises at least 5 wt. % of the silyl-containing compound.

19. The method of claim 11 , wherein the reaction is performed with a catalyst, a solvent, a pigment, or an additive.

20. The method of claim 11 , wherein the polyfunctional compound and the silyl-containing compound are applied to a substrate via spray, brush, roll, print, or dip method before a cross-linked thermoset is formed.

Assignees

• Us Gov Sec Navy

Inventors

• Iezzi Erick B
• Camerino Eugene
• Daniels Grant
• Wynne James H

Classifications

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C08G77/14

  containing silicon bound to oxygen-containing groups · CPC title

• C08J2375/04

  Polyurethanes · CPC title

• C08G18/73

  acyclic · CPC title

• C08G18/7893

  having three nitrogen atoms in the ring · CPC title